Method and structure for nanoimprint lithography masks using optical film coatings

ABSTRACT

Structures and associated methods for making smaller physical feature sizes for masks used in imprint lithography for application to patterning for advanced semiconductor and data storage devices.

RELATED APPLICATIONS

This application is a DIVISIONAL of U.S. application Ser. No.15/259,769, filed Sep. 8, 2016, which is a NONPROVISIONAL of and claimspriority to U.S. Provisional Application 62/234,798, filed Sep. 30,2015, each of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention is related to conformal surface coatings for masksused in imprint lithography for application to patterning for advancedsemiconductor and data storage devices; structures and associatedmethods for making high index of refraction surface coatings to improveproductivity, to reduce imprint mask defect levels and improveproductivity concurrently, and to achieve masks at smaller dimensionsare described.

BACKGROUND

Nano Imprint lithography (NIL) technology typically uses quartz maskswith nanometer feature sizes. The mask is placed above and in proximityto a wafer or workpiece coated with photosensitive material. The mask isthen closely coupled to the wafer, touching the photosensitive materialand drawing it into the features of the mask by capillary action andthen exposed to ultraviolet light. Then the mask is separated from theexposed photosensitive material and wafer, leaving behind nanometersized features on the wafer.

In order to promote the separation or release, fluorine terminatedsurfaces have been proposed (see U.S. Pat. No. 6,607,173), and toaddress both the release and fill requirements, a fractional fluorineterminated surface film, where the fraction may be continuously variedto achieve minimal defect conditions, has been proposed. Chemistriesused to deposit fractional F-terminated films use molecular monolayerdeposition from organo-silanes, with carbon backbones and fluorineterminations and are referred to herein as flurohydrocarbons or FHC's(see Seidel, T. E., et al., “Fluorine coatings for nanoimprintlithography masks,” Proceedings of the SPIE, “Alternative LithographicTechnologies VI” Volume 9049, February 2014, San Jose Calif.).

Many patents have been issued regarding NIL masks (see, e.g., U.S. Pat.Nos. 6,517,977, 7,384,569, 7,541,115, 7,776,709, 8,088,293, 8,097,539,8,178,011, and 8,273,505). Also prior work in this area has indicatedthat the surfaces of the quartz imprint mask may be uncoated (i.e.,clean quartz (crystalline SiO₂)) or may treated with surfactants orother chemicals (see U.S. Pat. Nos. 7,307,118, 7,452,574, and 7,837,921,and US PGPUBs 2005/0160934 and 2007/0212494). The placement offluoropolymer material on the surface of a mask using vapor depositionhas been described (US PGPUB 2007/0212494). Deposition of reactedflurohydrocarbon layers on ALD deposited Al₂O₃, deposited on polysiliconfor reduced sticking in MEMS devices has been described (U.S. Pat. No.6,562,553). Anti-reflection coatings using fluoropolymer blends havebeen described (U.S. Pat. No. 7,553,686). A comprehensive review paperof nano imprint lithography includes discussion of mask surfacetreatments (U.S. Pat. No. 5,198,267). The use of mixtures of misciblechemical precursors has been described for the purpose of makingHf_(x)Si_(1-x)O dielectric alloy thin (Schift, H., Imprint Lithography,“An old story in modern times, A Review,” J. Vac. Sci. Technol. B, Vol.26, No. 2, March/April 2008).

SUMMARY OF THE INVENTION

Optical intensity simulations, summarized below, indicate thepossibility that higher index coating materials affect an increase inthe intensity of exposure radiation in the region of the NIL maskfeature. In this disclosure, NIL mask designs are described usingconformal film coatings with a variety of indices of refraction.Coatings with higher indices of refraction providing higher intensitycan provide higher process productivity. Fractional F-terminated layersare combined with indices of refraction larger than the mask material toaffect both optimized fill and release and higher process productivity.Finally, the use of conformal coatings having the same or similaroptical parameters as the host mask material provides a method forreducing the feature sizes of NIL masks below that obtainable bycurrently available (e.g., electron beam) methods.

In one embodiment, a structure is proposed for a NIL mask using a hostmaterial (such as quartz, CaF₂ or other material), using processes knownin the art (such as electron beam, resist and etching processes) tofabricate features sizes and feature depths; the mask features are thenconformally coated with a film material or materials with a higher indexof refraction than the host material. The feature size of the mask, thetotal film thickness, and film index of refraction of the higher indexcoating materials are design parameters.

In another embodiment, multilayer conformal coatings on the NIL masksubstrate are used to achieve high index of refraction material (whichmay also be used to ensuring good chemical bonding) underneath asubsequently deposited fractional F-termination layer.

In another embodiment, conformal coatings using substantially the sameindex of refraction as the host mask material is used to reduce thefeature size of the mask.

Regarding the methods to achieve the embodiments, conformal layers canbe advantageously formed by Atomic Layer Deposition (ALD) processes asopposed to Chemical Vapor Deposition (CVD). However, CVD processes mayalso be used if the CVD process provides a conformal film which may beachieved if the sticking coefficient of the CVD reacting precursors islow.

One objective of the invention is to achieve a NIL mask having highindex of refraction material conformally placed on the imprint mask,using restrictive thickness for a given mask feature size andrestrictive index parameters for a given mask substrate index.

Another objective of the invention is to achieve a NIL mask having firsthigh index of refraction material on the imprint mask, followed by asecond layer of a molecular layer of a fractional fluorinatedhydrocarbon (FHC), using restrictive thicknesses for a given maskfeature size and restrictive index parameters for a given mask substrateindex.

Another objective of the invention is to achieve a smaller mask featuresize than otherwise possible by conformally coating the mask with amaterial having substantially the same optical parameters such as theindex of refraction and extinction coefficient as the host mask.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a structure of an imprint mask with a recessed featurehaving a conformal film chemically bonded to the mask surface with anindex of refraction greater than the imprint mask with the filmthickness shown as less than one half the mask feature size. Thephysical feature size is the mask feature size minus twice the filmthickness. The physical feature height is the same as the mask featureheight.

FIG. 2 shows a structure of an imprint mask with recessed featureshaving two multilayer and conformal films chemically bonded to the masksurface: one an underlayer abutting the mask surface and a top layer ofan FHC coating abutting to the top of the underlayer.

FIG. 3 shows a structure of a host imprint mask with a largercompensated feature size coated with a conformal film made from amaterial with substantially similar optical parameters as the host toachieve a smaller feature size.

DETAILED DESCRIPTION

Simulations of the optical intensity profiles within NIL mask featureshave been made for patterned quartz masks having ultrathin conformalfilm coatings with a variety on indices of refraction. Solutions usingTEMPESTpr2 and FDTH Maxwell solver software (SW) from PanoramicTechnology, Inc. were obtained for intensity profiles within the maskfeatures and explored for variances in the optical constants of thecoating films, feature size (FS), aspect ratio (AR), and wavelength, andcompared to a bare, uncoated mask reference.

Optical constants corresponding to quartz mask material and for Al₂O₃,TiO₂, and Si as example coating films were taken from the literature.These bulk values of optical constants are not expected to be the sameas actual ultra thin film values applied to the simulations. Thus, thesimulations are heuristic and semi-quantitative at best. The index ofrefraction values for the FHC films were assigned a range in an ad-hocmanner. The purpose of using these assigned optical constants is toprovide insight and guidance into trends and suggest possibilities.Wavelengths were varied from 193 nm to 365 nm. The question ofphoto-dissociation of the FHC layer for higher energy photons isaddressed from first principles Density Functional Theory (DFT) usingJaguar software (SW) from Schrodinger, Inc., with the result that theFHC layers are stable under exposure to higher wavelengths.

An outline of the results of the simulations is given here. First, theSW output for optical intensity for a reference case for 5 nm quartzmask feature size with no conformal coating(s) is simulated for opticalintensity at 365 nm. Following this, comparisons are made usingcompensated host mask sizes to obtain resultant 5 nm physical featuresizes having conformal coatings with a matrix of various indices ofrefraction. Simulations for smaller features sizes, various aspectratios and variances with exposure wavelengths follow. Finally,simulations for conformal coated features filled with resist overvarious substrates are simulated and partially optimized usingantireflection character of the underlying film system. The SW outputfor the intensity is given in relative ranges relative to the incominglevel set at 10. The scale is linear, so an intensity in the range of1-2 represents intensities from 10 to 20% and 3-4 is 30 to 40%, and soforth. Detailed results for the above can be seen in the publicationdescribing the simulations. (SPIE Photomask Conference Proceedings,Manuscript No. 9635-28, Monterey Calif., 2015.)

The intensity profile (intensity in the x-z plane within the feature)for bare, uncoated masks without resist, having mask feature size (MFS)of 5 nm and aspect ratio (AR) of 1 show a uniform intensity profile atthe 1-2 level. This 5 nm case with no coating is taken as a referencecase. The wavelength used is 365 nm and is used for all other casesunless stated otherwise) The index of refraction for the quartz is 1.47,with a k value of 0.001. This was compared to cases with assigned valuesof conformal coating materials with indices of refraction varying from1.3, 1.8 and 2.3 and k=0.001. A conformal film coating is defined as onehaving a constant thickness within ˜5% along the contour of the feature,for example as illustrated in FIG. 1. The mask with conformal coatingswas compensated up in size to give the same physical feature size (PFS)as the 5 nm control.

The intensity levels of the coated mask having the same 5 nm physicalfeature size as the control using an index or 1.3 show nominally thesame values as the uncoated mask. This might be expected since the indexfor the n=1.3 layer is not too different from the quartz (1.3 vs. 1.47).It is concluded that when the index of refraction for the conformalcoating is substantially the same (+/−˜15%) as the host mask, theoptical intensity profile in the feature is the same. This implies thatfeature sizes of NIL masks may be reduced by using conformal coatings oflike index materials. In the case of quartz (chemically SiO₂) made witha relatively large feature size could be conformally coated with ALDlayers of SiO₂. In the case of a NIL mask made from CaF₂ material, aconformal ALD coating of CaF₂ could be used. ALD processes for SiO₂ andmetal fluorides are available (see S. Yokoyama, et al. Appl. Phys. Lett.79, 617 (2001), and J. W. Klaus, et al. Surf. Rev. Lett. 6, 435 (1999);Younghee Lee and Steven M. George, et al, “Atomic Layer Deposition ofMetal Fluorides using various metal precursors and hydrogen fluoride,”Abstracts Technical Program and Abstracts of ALD15 Portland, 2015).While the ALD layers may not have the same exact micro-structure orimpurity content as the host mask material, their optical properties canbe similar enough to provide an optical match to the host mask. Any NILmasks can be coated with the same material of construction, or coatedwith a material with equivalent n and k optical parameters as the hostmask to make smaller controlled feature sizes.

When the coating index is increased from 1.3 to 1.8 and 2.3 (compared toa mask value of 1.47) the intensity is progressively increased near thefeature edges of the mask to the 3-4 level, while maintaining a 1-2level in the center of the mask. This implies use of a coating indexfilm with an index substantially higher than the mask index can increasethe intensity within the mask feature.

If two conformal layers are used, as illustrated in FIG. 2, consistingof an “underlayer” with indices of 3 and 6 and a top conformal layerwith an n value of 1.8, the intensities in the PFS are progressivelyhigher over larger (x,z) areas. For the combination n_(u)=1.8 andn_(t)=3, the intensity level is 3-4 over a third of the feature. Forn_(u)=1.8 and n_(t)=6, the intensity level is 3-4 over the entirecentral region spanning the x dimension and reaches the 5-6 level nearthe edges of the feature. Other combinations using an ad hoc value of2.3 for the top layer and 3 and 6 for the underlayer provides stillfurther progressively higher intensities within the feature. Thisimplies that combined conformal (multilayer films) having an underlayerindex substantially higher than the mask and a top layer substantiallythe same index as the mask (or higher) may increase the opticalintensity in the feature This indicates that the use of high indexconformal coatings used as underlayers, e.g., under an FHC layer, canhave higher intensities in the PFS, while also improving releasecharacteristics.

Intensity simulations were made for a variety of physical aspect ratios.The aspect ratio is defined as the feature depth divided by the featureinside width which is the space where resist may be placed. The AR'sranged from 0.7 to 2.85. For this set of simulations the wavelength was200 nm and the mask feature size was 5 nm. After conformal filmcoatings, the physical mask size was less than 5 nm. An intensity level3-4 over 80% of the physical feature cross sectional area was obtainedfor a 3.8 nm PFS, n=1.3 and AR=1.31. Intensity levels of 5-6 at thecenter and 6-7 level at the edge were obtained for a 3.4 nm PFS, n=1(top layer) and n=3 (underlayer) and AR=1.47. This implies thatmultilayer combinations with a modest index n=1.3 assigned for the toplayer and n=3 for the underlayer can yield significantly largeintensities, especially at smaller physical feature size. Intensitieswere 4-5 top and bottom and 5-6 in the center of the cross section for aphysical AR=2.85. AR-0.71, intensities were low and not much differentthan a control without a high index coating. These results imply betterintensities may be obtained as features get smaller and perhaps withincreasing aspect ratios.

Cases of AR ˜2 were simulated for mask features sizes of 8, 10 and 20nm, using 200 nm wavelength and index n=3 and compared to no layer indexon the mask. In all cases, there was essentially no difference in theintensity profiles between FHC and no FHC. The increased intensityeffect is operative for feature sizes of the order of 5 nm and less, butnot for feature sizes at 8 nm and above.

The wavelength dependence was addressed by comparing the intensityprofiles at 356 nm, 256 nm and 193 nm for various multilayercombinations. The optical constants assumed were n=1.3 (corresponding toan assigned FHC value) for the top layer and n=3 corresponding to bulkTiO₂, k=0.001 at all wavelengths for the underlayer and for bulk Si:n=6.5, k=2.71 at 365 nm; n=1.61, k=3.79 at 256 nm and n=0.88, k=2.78 at193 nm. For quartz, n=1.47 at 365 nm, 1.50 nm at 256, and n=1.56 at 193nm. Dispersion was used for Si and quartz indices. The physical featuresize for this comparison is 3.8 nm for the single coating of n=1.3 and aPFS=3.4 nm for the multilayer coatings with n=3 as underlayer and n=1.3on top, and n=6.5 as underlayer and n=1.3 on top. The corresponding ARfor the physical feature size is 1.31-1.38. In all cases the intensityprofile is non-uniform, but always higher than in the quartz outside themask feature. In summary at 365 nm, for a single layer coating, theintensity levels are 1-2 in the center and 3-4 at the edges of thefeature; for an underlayer with n=3 and a top layer of n=1.3 theintensity levels were 3-4 at the edges and center. For an underlayer ofn=6, and a top layer of 1.3, the intensity levels were 3-4 at the centerand 5-6 near the edges. For these cases the intensities increase withincreased index value for the underlayer.

First principles calculations for photo-dissociation were made for theligands of a proposed fluorine terminated molecule, the same layer thatis represented by ad-hoc assignment of an index 1.3, or 1.8 or 2.3.Density Functional Theory from the Materials Science Suite (MSS) fromSchrodinger Inc. provides a DFT code Jaguar and a workflow to calculatethe Bond Dissociation Energy (BDE). BDE values were calculated for 27ligands of both a F-terminated and non F-terminated amnosilanemolecules. The five possible C—H pairs had dissociation energies rangingfrom 98.43 to 106.8 kcal/mole. The two C—Si ligands had BDE values of93.5 and 94.06 kcal/mole. Conversions to corresponding wavelength usedthe relations: 23.1 kcal/mol=1 eV/molecule and E=hv, where h=4.13eVsec/molecule and v=c/free space wavelength. The wavelength is 310 nmfor the lowest BDE (93.5 kcal/mole) for breaking a C—Si bond.Wavelengths shorter than 310 nm may dissociate a variety of FHC ligands.As a result, the stable use of a FHC layers may be pursued usingexposure sources like the 356 nm i-line source.

Simulations using resist in the mask feature with underlying substratesshowed less intensity in the feature than those simulated for air cavityfeatures discussed above. Anti-reflection conditions were employed toincrease the intensity in the resist. A pattern transfer case wassimulated for making a hard mask of SiO₂ over Cu, and the thickness ofthe SiO₂ was varied to increase the intensity. AZ 1500 type resist at365 nm was used with its index of refraction and extinction coefficientfor an unexposed condition. For the condition of no coating and a PFS of5 nm, the intensity was uniform at the 1-2 level. An intensity level of2-3 was obtained when one conformal coating with an n=1.8 was used andthe mask was compensated to also provide a matched 5 nm PFS. For a toplayer FHC n=1.8 and a underlayer of n=6.5, having PFS=4.4 nm, theintensity near the bottom of the resist filled mask is at the 2-3 leveluniformly—in the x direction—across most of the bottom of the maskfeature and 3-4 near the lower edges of the mask. These increasedintensities may reduce exposure times. Even though the intensities arenon-uniform within the feature, if the increased intensity is uniformacross the width of the feature—as it is in this simulated case—theintegrity of the exposed resist feature may be maintained and theexposure process can be useful.

Several figures are used to connect the simulations to mask designs. InFIG. 1, a NIL mask (100) is illustrated, e.g., with a material ofconstruction of quartz, as may be patterned by electron beam methodsknown in the art to affect a “drawn” mask feature size (MFS) of widthdimension X (101) with depth dimension Z (102). The index of refractionn and extinction coefficient k for the mask's material of construction(104) at the wavelength of operation are known, e.g., for quartz:n=1.47, k=0.001 at 365 nm. A conformal film (106) with a different(advantageously) higher index of refraction, n_(h), and differentextinction coefficient, k_(h), characteristic of the conformal film ofthickness t_(h) (107) is deposited conformally over the mask feature.This results in a physical feature size width dimension of x=X−2t_(h)(108), since the conformal film encroaches on the width of the drawnmask width feature size on each surface of the feature. The depth isunchanged by the conformal coating, z=Z (102), as the feature's insidetop surface (110) is reduced by the same amount that is added to themask's external lower surface (110). The simulations indicate thatintensity is increased in the PFS when using a conformal coating ofindex greater than that of the NIL mask's material of construction. Thehigh index film thicknesses t_(h) will be less than half the maskfeature size. Mask feature sizes are less than 8 nm for the higherintensity to be effective.

In FIG. 2, a NIL mask (200) is illustrated, e.g., with a material ofconstruction of quartz, with a “drawn” mask feature size (MFS) of widthdimension X (201) with depth dimension Z (202). The index of refractionn and extinction coefficient k for the mask's material of construction(204) at the wavelength of operation are known at 365 nm. A conformalunderlayer film (206) with a higher index of refraction, n_(h), than thematerial of construction and possibly a different extinctioncoefficient, k_(h), characteristic of the conformal film of thicknesst_(h) is deposited conformally over the mask feature. In addition, aconformal F-terminated monomolecular layer is deposited as a top layeron the underlayer, having index of refraction n_(F), extinctioncoefficient k_(F), and thickness, t_(F). This allows a definition of thetotal conformal film thickness (207), t_(T)=t_(h)+t_(F) and the averageindex as n_(a)=(n_(h)t_(h)+n_(F)t_(F))/t_(T). This results in a physicalfeature size width dimension of x=X−2t_(T) (208). The depth is unchangedby the conformal coatings, z=Z (202), as the feature's inside topsurface (210) is reduced by the same amount that is added to the mask'sexternal lower surface (210). For the case of multilayer conformalfilms, the average index of refraction is designed to be greater thanthe NIL mask's material of construction and high total conformallaminate index film thicknesses t_(T) will be less than half the maskfeature size. Mask feature sizes are less than 8 nm for occurrence ofhigher exposure intensity inside the feature. The benefit of such adesign is to obtain higher process productivity and simultaneously lowerdefect density for NIL masks.

In FIG. 3, a general NIL host mask (300) with a minimum width dimensions(301) is shown with a feature size that is less than desired. Thematerial of construction has optical constants: index of refraction, nand extinction coefficient k, (304). The mask is conformally coated witha film (306) with thickness t_(s) (307) using a material havingsubstantially the same optical constants (304) as the host mask toenable the reduction of the feature size to a desired smaller value.(308). The index of refraction of the conformal film, n_(s), may besubstantially the same as the host mask, e.g n_(s)=n+/−15%. Thedifference in the k_(s) value relative to k may only be limited byattenuation by absorption of intensity due to the addition of theconformal coating film. This method and mask design provides a smallerwidth feature size (308) and does not change the depth (Z=z) of thefeature (302), as the film adds the same thickness to the interior andexterior surfaces (310), resulting in a new interior surface (309). Thedesired smaller targeted feature size (308) is x=X−2t_(s).

The absorption coefficient (alpha=k/wavelength) and the film's thicknessshould not reduce the incident intensity by more than a few percent forany of the applications discussed herein. The relationship: theextinction coefficient times the conformal film thickness(conservatively taken as the film's z dimension), divided by theexposure wavelength should be set at less than 0.05. This defines thecondition for the added conformal film not to substantially reduce theexposure intensity. For the case of two (or more) conformal films placedon the mask feature, the absorptions are in parallel and each film usesthe same above relation. The film material with the highest extinctioncoefficient dominates the loss of intensity.

In summary, optical intensity profiles in trenches of NIL coated maskswere simulated. The geometry, optical constants, wavelength and coatingson the trench features were varied. Mask design conditions for increasedexposure intensity are proposed. Use of a nanolaminate design withhigher index placed as an undercoating below a fractional FHC coating ofa moderate index of refraction are proposed for both lower fill andrelease defects as well as higher optical intensity and higher processproductivity. Finally, the concept that conformal films having the sameor substantially the same index of refraction as the host mask materialcan provide an approach for compensating the mask to obtain smallerfeature sizes than is currently available using standard methods.

What is claimed is:
 1. A nanolithography imprint host mask, comprisingmask features larger than desired, said host mask having an index ofrefraction and being coated with a conformal film material having anindex of refraction substantially the same as the host mask, wherein athickness of the conformal film is chosen as a difference between adesired mask feature size and twice the thickness of the conformal film,thereby to achieve a smaller desired mask physical feature size, and theconformal film having an extinction coefficient that does notsubstantially reduce an exposure intensity within the desired maskphysical feature size.
 2. The nanolithography imprint mask of claim 1,wherein the conformal film material coating has an index of refractionwithin 15% of an index of refraction of the host mask.
 3. Thenanolithography imprint mask of claim 1, wherein said mask featurescomprise mask features coated with at least a first underlayer conformalfilm material having substantially a same index of refraction as a maskmaterial index of refraction.
 4. The nanolithography imprint mask ofclaim 3, wherein said first underlayer is located under at least asecond top layer film having a fractional fluorinated termination. 5.The nanolithography imprint mask of claim 1, wherein the host mask ismade of quartz, and the conformal film material is amorphous SiO₂deposited by conformal ALD or CVD processes.
 6. The nanolithographyimprint mask of claim 1, wherein the host mask is made of CaF₂, and theconformal film material is substantially CaF₂ deposited by conformal ALDor CVD processes.
 7. The nanolithography imprint mask of claim 1,wherein the host mask is made of silicon (Si), and the conformal filmmaterial is silicon deposited by conformal ALD or CVD processes.
 8. Thenanolithography imprint mask of claim 1, wherein the host mask is madeof sapphire (AL₂O₃), and the conformal film material is Al₂O₃ depositedby conformal ALD or CVD processes.